β-naphthylalkylamines

ABSTRACT

Fungicidally active novel β-naphthylalkylamines of the formula ##STR1## in which Ar represents optionally substituted β-naphthyl and 
     R 1  and R 2 , which can be identical or different, represent alkyl or alkenyl or 
     R 1  and R 2 , together with the nitrogen atom to which they are bonded, represent an optionally substituted saturated heterocyclic radical, which can contain further hetero-atoms, 
     or plant-tolerated acid addition salts thereof.

The invention relates to new β-naphthylalkylamines, several processesfor their preparation and their use as fungicides.

It is already known that certain arylalkylamino compounds, such as, forexample, 1-(4-t-butylphenyl)-1-hydroxy-2-methyl-3-piperidin-1-yl-propanehydrochloride,1-(4-t-butylphenyl)-1-hydroxy-2-methyl-3-morpholin-4-yl-propanehydrochloride or1-(4-t-butylphenyl)-1-bromo-2-methyl-3-(2,6-dimethylmorpholin-4-yl)-propane,have fungicidal properties (compare, for example, DE-OS (GermanPublished Specification) No. 3,019,496).

However, the action of these compounds is not always completelysatisfactory in all fields of use under certain conditions, especiallywhen low amounts are applied and the concentrations are low.

New β-naphthylalkylamines of the general formula (I) ##STR2## in whichAr represents optionally substituted β-naphthyl and

R¹ and R², which can be identical or different, represent alkyl oralkenyl or

R¹ and R², together with the nitrogen atom to which they are bonded,represent an optionally substituted saturated heterocyclic radical,which can contain further hetero-atoms,

and acid addition salts thereof which are tolerated by plants, have beenfound.

It has furthermore been found that the new β-naphthylalkylamines of thegeneral formula (I) ##STR3## in which Ar represents optionallysubstituted β-naphthyl and

R¹ and R², which can be identical or different, represent alkyl oralkenyl or

R¹ and R², together with the nitrogen atom to which they are bonded,represent an optionally substituted saturated heterocyclic radical,which can contain further hetero-atoms,

and acid addition salts thereof which are tolerated by plants areobtained by a process in which (a) β-naphthylalkyl compounds of theformula (II) ##STR4## in which Ar has the abovementioned meaning and

X represents an electron-withdrawing leaving group,

are reacted with amines of the formula (III) ##STR5## in which R¹ and R²have the abovementioned meaning, if appropriate in the presence of adiluent and if appropriate in the presence of an acid-binding agent, orin which (b) the unsaturated aldehydes of the formula (IV) ##STR6## inwhich Ar has the abovementioned meaning, are reacted with amines of theformula (III) ##STR7## in which R¹ and R² have the abovementionedmeaning, in the presence of a reducing agent and, if appropriate, in thepresence of a catalyst, and, if appropriate, in the presence of adiluent, and, if appropriate, an acid is then added on.

It is also possible to quaternize the β-naphthylalkylamines of theformula (I) according to the invention on the nitrogen by generallycustomary methods to give the corresponding tetra-substituted ammoniumsalts.

Finally, it has been found that the new β-naphthylalkylamines of theformula (I) have fungicidal properties.

Surprisingly, the β-naphthylalkylamines of the formula (I) according tothe invention exhibit a considerably better fungicidal activity than thearylalkylamino compounds which are known from the prior art, such as,for example,1-(4-t-butylphenyl)-1-hydroxy-2-methyl-3-piperidin-1-yl-propanehydrochloride,1-(4-t-butylphenyl)-1-hydroxy-2-methyl-3-morpholin-4-yl-propanehydrochloride,1-(4-t-butylphenyl)-1-hydroxy-2-methyl-3-(2,6-dimethylmorpholin-4-yl)-propaneor1-(4-t-butylphenyl)-1-bromo-2-methyl-3-(2,6-dimethylmorpholin-4-yl)-propane,which are closely related compounds chemically and from the point ofview of their action.

Formula (I) provides a general definition of the β-naphthylalkylaminesaccording to the invention. Preferred compounds of the formula (I) arethose

in which

Ar represents β-naphthyl which is optionally mono-, di- ortri-substituted by identical or different substituents, possiblesubstituents being: halogen, hydroxyl and in each case straight-chain orbranched alkyl or alkoxy with in each case 1 to 6 carbon atoms, and

R¹ and R², which can be identical or different, represent in each casestraight-chain or branched alkyl or alkenyl with in each case up to 6carbon atoms, or

R¹ and R² , together with the nitrogen atom to which they are bonded,represent a saturated 5-membered to 7-membered heterocyclic radicalwhich can contain 1 or 2 further hetero-atoms, in particular nitrogen oroxygen, and is optionally mono-, di- or tri-substituted by identical ordifferent substituents, possible substituents being: in each casestraight-chain or branched alkyl or hydroxyalkyl with in each case 1 to4 carbon atoms.

Particularly preferred β-naphthylalkylamines of the formula (I) arethose

in which

Ar represents β-naphthyl which is optionally monosubstituted ordisubstituted by identical or different substituents, possiblesubstituents being: fluorine, chlorine, bromine, hydroxy, methyl, ethyl,n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxyand

R¹ and R², which can be identical or different, represent methyl, ethyl,n- or i-propyl, allyl, butenyl, dimethylallyl or n- or i-pentenyl, or

R¹ and R², together with the nitrogen atom to which they are bonded,represent a heterocyclic radical of the formula ##STR8## which isoptionally mono-, di- or tri-substituted by identical or differentsubstituents, possible substituents being: methyl, ethyl andhydroxymethyl.

The following β-naphthylalkylamines of the formula (I) may be mentionedspecifically, in addition to the compounds mentioned in the PreparationExamples:

    __________________________________________________________________________     ##STR9##                             (I)                                      Ar             R.sup.1                                                                          ##STR10##                                                  __________________________________________________________________________     ##STR11##     CH.sub.3                                                                          ##STR12##                                                   ##STR13##     -- --                                                                                         ##STR14##                                       ##STR15##     -- --                                                                                         ##STR16##                                       ##STR17##     -- --                                                                                         ##STR18##                                       ##STR19##     CH.sub.3                                                                          ##STR20##                                                   ##STR21##     -- --                                                                                         ##STR22##                                       ##STR23##     -- --                                                                                         ##STR24##                                       ##STR25##     -- --                                                                                         ##STR26##                                       ##STR27##     CH.sub.3                                                                          ##STR28##                                                   ##STR29##     -- --                                                                                         ##STR30##                                       ##STR31##     -- --                                                                                         ##STR32##                                       ##STR33##     CH.sub.3                                                                         CH.sub.2CHCH.sub.2                                           ##STR34##     -- --                                                                                         ##STR35##                                       ##STR36##     -- --                                                                                         ##STR37##                                       ##STR38##     -- --                                                                                         ##STR39##                                      __________________________________________________________________________

If, for example, 1-methanesulphonyloxy-2-methyl-3-β-naphthyl-propane and2,6-dimethylmorpholine are used as starting substances, the course ofthe reaction in process (a) according to the invention can berepresented by the following equation: ##STR40##

If, for example, 2-methyl-3-β-naphthyl-acrolein and3,5-dimethyl-piperidine are used as starting substances and hydrogen isused as the reducing agent, the course of the reaction in process (b)according to the invention can be represented by the following equation:##STR41##

Formula (II) provides a general definition of the β-naphthylalkylcompounds required as starting substances for carrying out process (a)according to the invention. In this formula (II), Ar preferablyrepresents those optionally substituted β-naphthyl radicals which havealready been mentioned as preferred for this radical in the descriptionof the substances of the formula (I) according to the invention. Xpreferably represents halogen, in particular chlorine, bromine oriodine, or in each case optionally substituted alkyl- oraryl-sulphonyloxy, in particular methanesulphonyloxy,trifluoromethanesulphonyloxy or p-toluenesulphonyloxy.

The β-naphthylalkyl compounds of the formula (II) are not yet known.

They are obtained by a process in which 2-methyl-3-β-naphthyl-acrylicacid esters of the formula (V) ##STR42## in which Ar has theabovementioned meaning and

R³ represents alkyl, in particular methyl or ethyl,

are initially reduced, in a first stage, with a reducing agent, such as,for example, lithium aluminum hydride, if appropriate in the presence ofa diluent, such as, for example, diethyl ether, at temperatures between-20° C. and +60° C., and the alcohols thus obtained, of the formula (VI)##STR43## in which Ar has the abovementioned meaning, are reacted toform derivatives by generally customary processes, thus, for example,are either sulphonated with sulphonic acid halides of the formula (VII)

    R.sup.4 --SO.sub.2 --Hal                                   (VII)

in which

R⁴ represents in each case optionally substituted alkyl or aryl, inparticular methyl, trifluoromethyl or p-tolyl, and Hal representshalogen, in particular chlorine or bromine,

if appropriate in the presence of a diluent, such as, for example,methylene chloride, and if appropriate in the presence of anacid-binding agent such as, for example, triethylamine, at temperaturesbetween -20° C. and +120° C., or are halogenated with halogenatingagent, such as thionyl chloride, phosphorus pentachloride, phosphorustribromide, hydrobromic acid or hydriodic acid, if appropriate in thepresence of a diluent, such as, for example, carbon tetrachloride, andif appropriate in the presence of a catalyst, such as, for example,pyridine, at temperatures between +20° C. and +180° C.

The 2-methyl-3-β-naphthylacrylic acid esters of the formula (V) areknown (compare, for example, Indian J. Chem. Section B, 22B (4), 352-354[1983] or J. org. Chemistry 33, 4351-4362 [1968]), or they can beprepared in a simple manner analogous to processes which are known inprinciple (compare, for example, J. Chem. Soc. 1961, 3160). Thesulphonic acid halides of the formula (VII) are generally knowncompounds of organic chemistry.

Formula (IV) provides a general definition of the unsaturated aldehydesrequired as starting substances for carrying out process (b) accordingto the invention. In this formula (IV), Ar preferably represents thoseoptionally substituted β-naphthyl radicals which have already beenmentioned as preferred for this radical in the description of thesubstances of the formula (I) according to the invention.

The unsaturated aldehydes of the formula (IV) are not yet known. Theyare obtained, however, by processes which are known in principle, inwhich β-naphthaldehydes of the formula (VIII) ##STR44## in which Ar hasthe abovementioned meaning, are reacted with propionaldehyde of theformula (IX) ##STR45## if appropriate in the presence of a diluent, suchas, for example, methanol, and if appropriate in the presence of acatalyst, such as, for example, sodium hydroxide, at temperaturesbetween -20° C. and +120° C., and water is split off from the additionproducts thus obtainable, of the formula (X) ##STR46## in which Ar hasthe abovementioned meaning,

likewise in a generally customary manner, with an acid catalyst, suchas, for example, acetic acid, if appropriate in the presence of adiluent, such as, for example, methanol, at temperatures between +20° C.and 180° C.

The β-naphthaldehydes of the formula (VIII) and propionaldehyde of theformula (IX) are generally known compounds of organic chemistry.

Formula (III) provides a general definition of the amines furthermorerequired as starting substances for carrying out processes (a) and (b)according to the invention. In this formula (III), R¹ and R² preferablyrepresent those radicals which have already been mentioned as preferredfor these substituents in the description of the substances of theformula (I) according to the invention.

The amines of the formula (III) are likewise generally known compoundsof organic chemistry.

Possible diluents for carrying out process (a) according to theinvention are inert organic solvents.

These include, in particular, aliphatic or aromatic, optionallyhalogenated hydrocarbons, such as, for example, benzine, benzene,toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane,methylene chloride, chloroform and carbon tetrachloride, ethers, such asdiethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ordiethyl ether, ketones, such as acetone or butanone, nitriles, such asacetonitrile or propionitrile, amides, such as dimethylformamide,dimethylacetamide, N-methylformanilide, N-methylpyrrolidone orhexamethylphosphoric acid triamide, esters, such as ethyl acetate, orsulphoxides, such as dimethylsulphoxide. However, the reaction can alsobe carried out without diluents.

If appropriate, process (a) according to the invention can be carriedout in the presence of an acid-binding agent.

Possible acid-binding agents are all the usual inorganic or organicbases. These include, for example, alkali metal hydroxides, such assodium hydroxide or potassium hydroxide; alkali metal carbonates, suchas sodium carbonate, and tertiary amines, such as triethylamine,N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine,diazabicyclooctane (DABCO), diazabicyclonone (DBN) ordiazabicycloundecene (DBU).

An appropriate excess of amine of the formula (III) used as the reactantcan simultaneously serve as the acid-binding agent and, if the amine isin liquid form, also as the diluent.

The reaction temperatures can be varied within a substantial range incarrying out process (a) according to the invention. In general, thereaction is carried out at temperatures between 0° C. and 250° C.,preferably at temperatures between 30° C. and 180° C.

For carrying out process (a) according to the invention, in general 1.0to 10.0 moles, preferably 1.0 to 5.0 moles, of amine of the formula(III) and, if appropriate, 1.0 to 10.0 moles, preferably 1.0 to 5.0moles, of acid-binding agent are employed per mole of β-naphthylalkylcompound of the formula (II). For working up, the reaction product isseparated off from water-soluble impurities by partition in anaqueous-organic two-phase system, and is isolated in the generallycustomary manner and then, if appropriate, purified by columnchromatography.

Possible diluents for carrying out process (b) according to theinvention are likewise inert organic solvents.

These include, in particular, aliphatic or aromatic, optionallyhalogenated hydrocarbons, such as, for example, benzine, benzene,toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane,methylene chloride, chloroform and carbon tetrachloride, ethers, such asdiethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ordiethyl ether, or alcohols, such as methanol, ethanol or isopropanol.However, the reaction can also be carried out without diluents.

Possible reducing agents are all the usual compounds which reducecarbonyl groups. Molecular hydrogen of formic acid is preferably used.

Possible catalysts are likewise all the usual hydrogenation catalysts.Noble metal, noble metal oxide or noble metal hydroxide catalysts orso-called Raney catalysts, in particular platinum, platinum oxide andRaney nickel, are preferably used.

The reaction temperatures can be varied within a substantial range incarrying out process (b) according to the invention. In general, thereaction is carried out at temperatures between 0° C. and +250° C.,preferably at temperatures between +20° C. and +200° C.

Process (b) according to the invention can be carried out under normalpressure or under increased pressure. In general, it is carried outunder between 1 atmosphere and 300 atmospheres, preferably between 1atmosphere and 200 atmospheres.

For carrying out process (b) according to the invention, in general 1.0to 5.0 moles, preferably 1.0 to 2.0 moles, of amine of the formula (III)and 1.0 to 10 moles, preferably 1.0 to 5.0 moles, of reducing agent and,if appropriate, 0.01 to 0.1 mole of catalyst are employed per mole ofunsaturated aldehyde of the formula (IV). The compounds of the formula(I) are worked up and isolated in the generally customary manner.

If appropriate, the compounds of the formula (I) according to theinvention can then be converted into acid addition salts.

The following acids can preferably be used for the preparation ofphysiologically acceptable acid addition salts of the compounds of theformula (I): the hydrogen halide acids, such as, for example,hydrochloric acid and hydrobromic acid, in particular hydrochloric acid,and furthermore phosphoric acid, nitric acid, sulphuric acid,monofunctional, bifunctional and trifunctional carboxylic acids andhydroxycarboxylic acids, such as, for example, acetic acid, maleic acid,succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid,sorbic acid and lactic acid, and sulphonic acids, such as, for example,p-toluenesulphonic acid and 1,5-naphthalenedisulphonic acid.

The acid addition salts of the compounds of the formula (I) can beobtained in a simple manner by customary salt formation methods, forexample by dissolving a compound of the formula (I) in a suitable inertsolvent and adding the acid, for example hydrochloric acid, and they canbe isolated in a known manner, for example by filtration, and ifappropriate purified by washing with an inert organic solvent.

The active compounds according to the invention exhibit a powerfulmicrobicidal action and can be employed in practice for combatingundesired micro-organisms. The active compounds are suitable for use asplant protection agents.

Thus, for example, fungicidal agents are employed in plant protectionfor combating Plasmodiophoromycetes, Oomycetes, Chytridiomycetes,Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

The active compounds according to the invention can be used withparticularly good success for combating cereal diseases, such as, forexample, against the leaf spot of wheat causative organism(Leptosphaeria nodorum), against the stripe disease of barley causativeorganism (Drechslera graminea), against the net blotch disease of barleycausative organism (Pyrenophora teres) and against the powdery mildew ofcereal causative organism (Erysiphe graminis), for combating ricediseases, such as, for example, against the rice spot disease causativeorganism (Pyricularia oryzae), or for combating vegetable diseases, suchas, for example, against the powdery mildew of cucumber causativeorganism (Sphaerotheca fuliginea). Besides an outstanding protectiveactivity, the active compounds according to the invention also exhibitextremely good systemic properties.

The active compounds can be converted to the customary formulations,such as solutions, emulsions, suspensions, powders, foams, pastes,granules, aerosols, very fine capsules in polymeric substances and incoating compositions for seed, as well as ULV formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water. By liquefied gaseous extenders orcarriers are meant liquids which are gaseous at normal temperatures andunder normal pressure, for example aerosol propellants, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide. As solid carriers there are suitable: for example groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly-disperse silicic acid, alumina and silicates.As solid carriers for granules there are suitable: for example crushedand fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, as well as synthetic granules of inorganic andorganic meals, and granules of organic material such as sawdust, coconutshells, corn cobs and tobacco stalks. As emulsifying and/or foam-formingagents there are suitable: for example non-ionic and anionicemulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products. As dispersing agents there are suitable:for example ligninsulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 percent by weightof active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in theformulations as a mixture with other known active compounds, such asfungicides, insecticides, acaricides and herbicides, and as mixtureswith fertilizers and growth regulators.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, emulsifiable concentrates, emulsions, foams, suspensions,wettable powders, pastes, soluble powders, dusting agents and granules.They are used in the customary manner, for example by watering,spraying, atomizing, scattering, dusting, foaming, brushing on and thelike. It is furthermore possible to apply the active compounds by theultralow volume method or to inject the active compound formulation orthe active compound itself into the soil. The seeds of the plants canalso be treated.

In the treatment of parts of plants, the active compound concentrationsin the use forms can be varied within a substantial range. They are ingeneral between 1 and 0.0001% by weight, preferably between 0.5 and0.001%.

In the treatment of seed, amounts of active compound of 0.001 to 50 gper kilogram of seed, preferably 0.01 to 10 g, are generally required.

For the treatment of soil, active compound concentrations of 0.00001 to0.1% by weight, preferably 0.0001 to 0.2%, are required at the place ofaction.

PREPARATION EXAMPLES Example 1 ##STR47##

10.8 g (0.04 mole) of1-methanesulphonyl-2-methyl-3-β-naphthyl-propaneand 9 g (0.078 mole) of cis-2,6-dimethylmorpholine are stirred at a bathtemperature of 140° C. for 15 hours. Water is added to the resultingreaction mixture and the mixture is extracted several times with ether.The combined organic phases are dried over sodium sulphate and freedfrom the solvent in vacuo; the oily residue is purified by columnchromatography (silica gel 60/petroleum ether-ether 2:1). 6.2 g (52% oftheory) ofcis-1-(2,6-dimethylmorpholin-4-yl)-2-methyl-3-β-naphthyl-propane ofrefractive index n_(D) ²⁰ : 1.5527 are obtained.

Preparation of the starting compound ##STR48##

11 g (0.1 mole) of methanesulphonyl chloride are added dropwise to 14 g(0.074 mole) of 2-methyl-3-β-naphthyl-propanol (crude) in 80 ml ofabsolute pyridine at 0° C., with stirring, the mixture is stirred for afurther 16 hours at room temperature when the addition has ended, excesspyridine is removed by distillation in vacuo, the residue is taken up inwater, the mixture is extracted several times with methylene chloride,the extract is dried over sodium sulphate and the solvent is removed invacuo. 13.6 g (66% of theory) of1-methanesulphonyloxy-2-methyl-3-β-naphthyl-propane are obtained as anoil. (IR: γ=1345 and 1180 cm⁻¹). ##STR49##

12 g (0.05 mole) of ethyl 2-methyl-3-β-naphthylacrylate are addeddropwise to a suspension of 1.9 g (0.05 mole) of lithium aluminumhydride in 150 ml of absolute ether in a dry nitrogen atmosphere, whilecooling with ice. When the addition has ended, the mixture is warmed atthe reflux temperature for 8 hours and, after the reaction mixture hasbeen cooled, 15 ml of 5 percent strength sulphuric acid are then slowlyadded dropwise, with cooling, the solid which has precipitated isfiltered off with suction, the filtrate is dried over sodium sulphate,the solvent is removed in vacuo and the residue is recrystallized fromether/petroleum ether. 7.1 g of 2-methyl-3-β-naphthyl-propanol ofmelting point 71°-74° C. which, according to the gas chromatogram, iscontaminated with 2-methyl-1-β-naphthyl-propen-3-ol and can be used inthe next reaction stage without further purification, are obtained.##STR50##

40 g (0.2 mole) of ethyl β-ethoxalylpropionate are added to a suspensionof 5.5 g (0.2 mole) of 80% pure sodium hydride in 300 ml of absolutexylene at 70° C. When the evolution of hydrogen has ended, 31.2 g (0.2mole) of β-naphthaldehyde, dissolved in xylene, are added dropwise and,when the addition has ended, the mixture is heated at the boiling pointfor 90 minutes.

150 ml of water are added to the cooled reaction mixture, and theorganic phase is separated off, washed with 7% strength sodium carbonatesolution, dried over sodium sulphate and concentrated. The residue isdistilled in vacuo. 21.7 g (45.2% of theory) of ethyl2-methyl-3-β-naphthyl-acrylate of boiling point 110° C./0.13 mbar areobtained.

Example 2

Analogously to Example 1 there can be prepared the compound ##STR51##with the refractive index n_(D) ²⁰ : 1.5547.

USE EXAMPLES

The compounds shown below are employed as comparison substances in theuse examples which follow: ##STR52##1-(4-t-Butylphenyl)-1-hydroxy-2-methyl-3-piperidin-1-yl-propanehydrochloride ##STR53##1-(4-t-Butylphenyl)-1-hydroxy-2-methyl-3-morpholin-4-yl-propanehydrochloride ##STR54##1-(4-t-Butylphenyl)-1-hydroxy-2-methyl-3-(2,5-dimethylmorpholin-4-yl)-propane##STR55##1-Bromo-1-(4-t-butylphenyl)-2-methyl-3-(2,6-dimethylmorpholin-4-yl)-propane(all known from DE-OS (German Published Specification) No. 3,019,496)

Example A Leptosphaeria nodorum test (wheat)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a conidia suspension ofLeptosphaeria nodorum. The plants remain in an incubation cabinet at 20°C. and 100% relative atmospheric humidity for 48 hours.

The plants are placed in a greenhouse at a temperature of about 15° C.and a relative atmospheric humidity of about 80%.

Evaluation is carried out 10 days after the inoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compound according to preparation Example 1.

Example B Pyrenophora teres test (barely)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a conidia suspension ofPyrenophora teres. The plants remain in an incubation cabinet at 20° C.and 100% relative atmospheric humidity for 48 hours.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%.

Evaluation is carried out 7 days after the inoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compound according to preparation Example 1.

Example C Drechslera graminea test (barley)/seed treatment (syn.Helminthosporium gramineum)

The active compounds are used as dry dressings. These are prepared byextending the particular active compound with a ground mineral to give afinely pulverulent mixture, which ensures uniform distribution on theseed surface.

To apply the dressing, the infected seed is shaken with the dressing ina closed glass flask for 3 minutes.

The seed is embedded in sieved, moist standard soil and is exposed to atemperature of 4° C. in closed Petri dishes in a refrigerator for 10days. Germination of the barley, and possibly also of the fungus spores,is thereby initiated. 2 batches of 50 grains of the pregerminated barleyare subsequently sown 3 cm deep in standard soil and are cultivated in agreenhouse at a temperature of about 18° C., in seedboxes which areexposed to light for 15 hours daily.

About 3 weeks after sowing, the plants are evaluated for symptoms ofstripe disease.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compound according to preparation Example 1.

Example D Sphaerotheca test (cucumber)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are dusted with conidia of the fungusSphaerotheca fuliginea.

The plants are then placed in a greenhouse at 23° to 24° C. and at arelative atmospheric humidity of about 75%.

Evaluation is carried out 10 days after the inoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compound according to preparation Example 1.

Example E Pyricularia test (rice)/systemic

Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent, and theconcentrate is diluted with water and the stated amount of emulsifier,to the desired concentration.

To test for systemic properties, standard soil in which young riceplants have been grown is watered with 40 ml of the preparation ofactive compound. 7 days after the treatment, the plants are inoculatedwith an aqueous spore suspension of Pyricularia oryzae. Thereafter, theplants remain in a greenhouse at a temperature of 25° C. and a relativeatmospheric humidity of 100% until they are evaluated.

Evaluation of the disease infestation is carried out 4 days after theinoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compound according to preparation Example 1.

It will be understood that the specification and examples areillustrative but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

We claim:
 1. A β-naphthylalkylamine of the formula ##STR56## in which Arrepresents β-naphthyl which is optionally mono-, di- or tri-substitutedby identical or different substituents from the group comprising halogenand alkyl and alkoxy with in each case 1 to 6 carbon atoms, andR¹ andR², together with the nitrogen atom to which they are bonded, representa heterocyclic radical of the formula ##STR57## which is optionallymono-, di- or tri-substituted by identical or different substituentsfrom the group comprising in each case straight-chain or branched alkyland hydroxyalkyl with in each case 1 to 4 carbon atoms,or aplant-tolerated acid addition salt thereof.
 2. A β-naphthylalkylamine orsalt according to claim 1, in whichAr represents β-naphthyl which isoptionally mono-substituted or disubstituted by identical or differentsubstituents from the group comprising fluorine, chlorine, bromine,hydroxy, methyl, ethyl, n- or i-propyl, n-, i-, s- or t.-butyl, methoxy,ethoxy and n- or i-propoxy, and R¹ and R², which can be identical ordifferent, represent methyl, ethyl, n- or i-propyl, allyl,dimethylallyl, butenyl or n- or i-pentenyl, or R¹ and R², together withthe nitrogen atom to which they are bonded, represent a heterocyclicradical of the formula ##STR58## which is optionally mono-, di- ortri-substituted by identical or different substituents from the groupcomprising methyl, ethyl and hydroxymethyl.
 3. A compound according toclaim 1, wherein such compound is1-(2,6-dimethylmorpholin-4-yl)-2-methyl-3-β-naphthyl-propane of theformula ##STR59## or a plant-tolerated acid addition salt thereof.
 4. Acompound according to claim 1, wherein such compound is2-methyl-1-(3-methyl-piperidin-1-yl)-3-β-naphthyl-propane of the formula##STR60## or a plant-tolerated acid addition salt thereof.
 5. Afungicidal composition comprising a fungicidally effective amount of acompound or salt according to claim 1 in admixture with a diluent.
 6. Aβ-naphthylalkylamine or salt according to claim 2,in which Ar representsβ-naphthyl which is optionally mono-substituted or di-substituted bymethyl, ethyl, n- or i-propyl or n-, i-, s- or ti-butyl, R¹ and R²together with the nitrogen atom to which they are bonded, represent aheterocyclic radical of the formula ##STR61## which is optionally mono-,di- or tri-substituted by identical or different substituents from thegroup comprising methyl, ethyl and hydroxymethyl.